KR20010095050A - Dielectric ceramic composition, ceramic capacitor using the composition and process of producing same - Google Patents

Abstract

PURPOSE: A dielectric ceramic composition and manufacturing method of ceramic capacitors using the composition are provided. The ceramic composition having excellent dielectric properties(low dielectric loss, high dielectric constant and stable temperature characteristics) in the range of high frequency enables low temperature sintering so that it can save manufacturing cost. CONSTITUTION: The composition comprises SrxBa(1-x)(ZryTi(1-y))O3 as a main component, 0.05-15wt.% of MnO2, 0.001-5wt.% of one or more kinds of Bi2O3, PbO, Sb2O3, and 0.5-15wt.% of glass composition in ZnO-SiO2 system or LiO2-Al2O3-SiO2 system, where 0.8<=x<=1, 0.9<=y<=1. The multilayered ceramic capacitors are produced through a conventional process, ball-milling, forming to a dielectric sheet(11), forming an electrode(12) made of non-metallic or carbon-based materials, multi-layering the sheets, pressing and sintering at 925-1080deg.C in a reductive(N2-H2) or inert gas atmosphere.

Description

Dielectric ceramic composition, magnetic capacitor using same and method for manufacturing the same {Dielectric ceramic composition, ceramic capacitor using the composition and process of producing same}

The present invention relates to a dielectric magnetic composition, a magnetic capacitor using the same, and a method of manufacturing the same. Particularly, the present invention relates to a dielectric material having low dielectric loss in a high frequency band and stable properties, and furthermore, to achieve low temperature firing and to produce copper (Cu), Non-metals such as tungsten (W), or carbon-based materials such as carbon and graphite can be used, and as a result, a dielectric magnetic composition that enables a significant reduction in manufacturing cost and a cost reduction of a product, A magnetic capacitor and a method of manufacturing the same.

Background Art Conventionally, ceramic capacitors using dielectric characteristics of ceramics are known as small and large capacity capacitors. The ceramic capacitor is made of a capacitor having a dielectric material, one or a desired combination of properties thereof, such as rutile (rutile) Type of TiO _2, the perovskite-type of _{MgTiO 3, CaTiO 3, SrTiO 3} .

Ceramic capacitors are classified into single layer type and stacked type.

The single-layer ceramic capacitor is press-molded the above-described material powder to form a molded body such as pellets (plates), rods (cylindrical), chips (squares), and the like, and the molded body is formed at a temperature of 1200 to 1400 ° C in air. It can be obtained by firing to form a sintered body and forming electrodes on both surfaces of the sintered body.

In addition, the multilayer ceramic capacitor is kneaded with the above-described material powder, an organic binder and an organic solvent to form a slurry. The slurry is formed on a sheet by a doctor blade method and degreased to form a green sheet. After printing an electrode made of a noble metal such as Pt or Pd on the green sheet, these green sheets are laminated in the thickness direction and pressurized to form a laminate, and the laminate is obtained by firing at a temperature of 1200 to 1400 캜 in the air. Can be.

By the way, in the above-mentioned conventional ceramic capacitor, baking at the high temperature of 1200-1400 degreeC is needed in order to obtain the compact sintered compact which is excellent in electrical characteristics.

In particular, in the multilayer ceramic capacitor, when the base metal is used as the electrode material, the base metal is oxidized at the time of firing to form a high resistance layer between the ceramic layers. Therefore, it is necessary to use a precious metal material such as Pt or Pd that is stable even at high temperatures. There was a difficult problem.

In addition, when applied to a high frequency region such as microwaves, it is desirable to have a low dielectric loss, and higher characteristics and higher reliability are required for electrical characteristics such as temperature characteristics and quality factor (Q). However, current dielectric materials do not satisfy these requirements.

In view of the above circumstances, the present invention has a stable characteristic with low dielectric loss in the high frequency band, and furthermore, it is possible to realize firing at a low temperature and to use a nonmetal or a carbon-based material as an electrode material. It is an object of the present invention to provide a dielectric magnetic composition, a magnetic capacitor using the same, and a method of manufacturing the same, which can significantly reduce the cost of the product.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the single-layer ceramic capacitor which is 1st Embodiment of this invention.

It is sectional drawing which shows the multilayer ceramic capacitor which is 2nd Embodiment of this invention.

* Description of the symbols for the main parts of the drawings *

Bulk dielectric 2 ..... Terminal electrode

3 ..... lead wire 4 ..... epoxy resin

11 ..... Dielectric layer 12 ..... Internal electrode

13, 14 ..... Terminal electrode

In order to solve the above problems, the present invention provides a dielectric magnetic composition, a magnetic capacitor using the same, and a method of manufacturing the same.

That is, the dielectric magnetic composition according to the present invention is MnO ₂ in a casting formed of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ ₁ and 0.9 ≦ _y ≦ 1). 0.05 to 15% by weight, one or two or more selected from Bi ₂ O ₃ , PbO, Sb ₂ O _{3 It} is characterized by consisting of 0.001 to 5% by weight, 0.5-15% by weight of the glass composition.

This dielectric magnetic composition is composed of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ ₁ and 0.9 ≦ _y ≦ 1), with 0.05 to 15 weights of MnO ₂ . High relative dielectric constant, good temperature characteristic and high quality factor by adding 0.001 to 5% by weight of one or two or more selected from%, Bi ₂ O ₃ , PbO, Sb ₂ O ₃ and 0.5-15% by weight of the glass composition Is feasible. As a result, the characteristics are stable in the high frequency region such as microwaves, and the reliability is improved in the high frequency region.

Here, the molar ratio of Sr is 0.8 or more (80 mol% or more) because when it is baked at less than 0.8 (less than 80 mol%) at a low temperature of 925 to 1080 ° C, the sinterability is lowered and a good sintered body cannot be obtained.

The molar ratio of Ti is 0.1 or less (10 mol% or less) because when the temperature exceeds 0.1 (10 mol%), the quality factor Q decreases and the temperature characteristic becomes negative.

MnO ₂ is added as a sintering agent because it enables the first low-temperature co-fired, the addition amount is preferably 0.05~15% by weight. The reason for this is that when the added amount is less than 0.05% by weight, there is no addition effect, and therefore, a compact sintered body cannot be obtained at low temperature firing, and when it exceeds 15% by weight, the quality factor Q is lowered.

One or two or more low-melting metal oxides selected from Bi ₂ O ₃ , PbO, and Sb ₂ O ₃ are added to improve the temperature characteristics, and the amount thereof is preferably 0.001 to 5% by weight. The reason is that when the added amount is less than 0.001% by weight, the effect of improving the temperature characteristic is not obtained, and when the amount exceeds 5% by weight, the quality factor Q is lowered.

Since the glass composition enables low-temperature baking of 925-1080 degreeC, it is added as a sintering adjuvant, The addition amount is 0.5 to 15 weight% is preferable. The reason is that if the added amount is less than 0.5% by weight, it is not effective as a sintering aid, and therefore, it cannot be baked at low temperature. As a result, the relative dielectric constant, temperature characteristics, and quality coefficient are lowered. This is because Q) decreases.

The glass composition does not adversely affect properties even if added, and the wettability of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ 1 and 0.9 ≦ _y ≦ ₁ ), which is a main composition, It is preferable that the glass soften and / or melt at a temperature of 925 to 1080 ° C. Specifically, ZnO-SiO ₂ -based glass, Li ₂ O-Al ₂ O ₃ -SiO ₂ -based glass, and the like are preferable.

The dielectric magnetic composition according to the present invention is characterized in that the dielectric ceramic composition is prepared by adding 0.01-5% by weight of SiO ₂ and 0.01-5% by weight of Al ₂ O ₃ to the cast product.

SiO ₂ is added to improve the temperature characteristic, and the amount thereof is preferably 0.01 to 5% by weight. The reason for this is that when the added amount is less than 0.01% by weight, the effect of improving the temperature characteristics is not obtained, and when the amount is more than 5% by weight, the quality factor Q decreases.

Al ₂ O ₃ is added to improve the quality factor (Q), and the amount thereof is preferably 0.01-5% by weight. This is because when the amount added is less than 0.01% by weight, the effect of improving the quality factor Q is not obtained, and when the amount is more than 5% by weight, the temperature characteristic is lowered.

In addition, the dielectric ceramic composition according to the present invention is characterized in that the dielectric ceramic composition is obtained by adding 0.001-2% by weight of rare earth oxide to the cast product.

The rare earth oxide is added to improve the temperature characteristics, and the amount thereof is preferably 0.001 to 2% by weight. The reason for this is that when the added amount is less than 0.001% by weight, the effect of improving the temperature characteristics is not obtained, and when the amount exceeds 2% by weight, the quality factor Q is lowered.

As rare earth oxides, Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (0.8 ≤ _{x ≤ 1} , 0.9 ≤ _y ≤ 1), which is a cast product, have good wettability and are present in the grain boundary layer. It is preferable to improve sinterability. Specifically, La ₂ O ₃ , CeO ₂ , Pr ₆ O ₁₁ , Nd ₂ O ₃ , Sm ₂ O ₃ , Dy ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , Tm ₂ O ₃ , Yb ₂ O It is preferable to combine one or two or more selected from _three .

The magnetic capacitor according to the present invention is characterized in that the electrode is formed on both sides of the element made of the above-described dielectric magnetic composition.

The magnetic capacitor according to the present invention is characterized by alternately stacking a sheet-like dielectric composed of the above dielectric magnetic composition and an electrode.

In addition, the magnetic capacitor according to the present invention is characterized in that in the above capacitor, the electrode is made of a non-metal or carbon-based material.

This magnetic capacitor has a stable characteristic with low dielectric loss in the high frequency band by using the above dielectric magnetic composition. This improves the reliability, especially in the high frequency band.

In addition, by using the above dielectric ceramic composition, it is possible to bake at a low temperature of 925 to 1080 占 폚. As a result, manufacturing cost can be reduced by using an inexpensive nonmetal or carbon-based material as the internal electrode.

As the base metal, one or two or more selected from metals having high characteristics as conductors and high reliability, such as copper (Cu), nickel (Ni), tungsten (W), and molybdenum (Mo), may be used. Metal containing is preferable.

As the carbonaceous substance, carbon (amorphous carbon), graphite (quartz, graphite), or a mixture thereof is preferable.

According to the present invention, there is provided a method for producing a dielectric magnetic composition comprising MnO in a casting formed of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ ₁ and 0.9 ≦ _y ≦ 1). ₂ to 0.05 to 15% by weight, one or two or more selected from Bi ₂ O ₃ , PbO, Sb ₂ O ₃ or 0.001 to 5% by weight of the powder composition, 0.5-15% by weight of the glass composition is molded and bulked It is set as a shaped object of sheet shape or a sheet, and this molded object is baked at the temperature of 925-1080 degreeC, It is characterized by the above-mentioned.

In the method of manufacturing the dielectric magnetic composition, MnO ₂ is 0.05 in a casting formed of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ ₁ and 0.9 ≦ _y ≦ 1). 15-15% by weight, one or two or more selected from Bi ₂ O ₃ , PbO, Sb ₂ O ₃ , 0.001 to 5% by weight, and a glass composition added 0.5-15% by weight of the powder is molded into a bulk or sheet The molded article was formed into a phase, and the molded article was fired at a temperature of 925 to 1080 ° C. to improve the wettability of the grain boundary layer during the low temperature firing process of sintering aid of MnO ₂ and the glass composition to bond powder particles in the molded body. In addition to sintering, the sintering is performed while reducing the voids of the powder particles. As a result, even when fired at a low temperature of 925 to 1080 ° C., a compact high strength sintered compact can be obtained.

Further, in the method of manufacturing the dielectric magnetic composition according to the present invention, in the method of manufacturing the dielectric magnetic composition, an electrode is formed on one main surface of the sheet-shaped molded body, and then the molded bodies are laminated in a plurality of thickness directions and pressed. To obtain a laminate, and the laminate is calcined at the above temperature.

In the method for producing a dielectric self-composition, an electrode is formed on one main surface of a sheet-like molded article, and then the molded articles are laminated in a plurality of thickness directions, pressurized to form a laminate, and then the laminate is fired at the above temperature. As the internal electrode material, inexpensive non-metals such as Cu and Ni, or carbon-based materials such as amorphous carbon and graphite can be used as compared with precious metals of Pt and Pd. As a result, the cost can be reduced without lowering the characteristics.

Embodiments of the dielectric magnetic composition of the present invention, a magnetic capacitor using the same, and a method of manufacturing the same will be described with reference to the drawings.

[First Embodiment]

1 is a cross-sectional view showing a ceramic capacitor (magnetic capacitor) according to a first embodiment of the present invention, in which, reference numeral 1 denotes a bulk dielectric, 2 a terminal electrode formed on both sides of the dielectric 1, and 3 a terminal electrode ( The lead wire 4 connected to 2) is an epoxy resin for sealing the dielectric 1 and the terminal electrode 2.

The dielectric material 1 is formed of a casting formed of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ ₁ and 0.9 ≦ _y ≦ 1) (hereinafter only referred to as SBZT). , 0.05-15% by weight of MnO ₂ , 0.001-5% by weight of one or two or more selected from Bi ₂ O ₃ , PbO, Sb ₂ O ₃ , and 0.5-15 of glass frit (glass composition). A dielectric ceramic composed of a material composition added by weight%.

The material composition of the dielectric 1 is a material composition in which 0.01-5% by weight of SiO ₂ and 0.01-5% by weight of Al ₂ O ₃ are added to the cast product, or 0.001-2% by weight of rare earth oxide in the cast product. The added material composition or the cast composition may be any one of 0.01-5% by weight SiO ₂ , 0.01-5% by weight Al ₂ O _3, and 0.001-2% by weight rare earth oxide.

The terminal electrode 2 is composed of an electrode material having high characteristics as a conductor and having high reliability, for example, Ag or Ag alloy. As the Ag alloy, for example, 90Ag-10Pd is suitable.

Instead of Ag or Ag alloy, for example, Cu, Ni, W or Mo, or an alloy containing two or more thereof, or carbon, graphite, or a mixture thereof may be used.

In this ceramic capacitor, the relative dielectric constant (ε), quality factor (Q), and temperature characteristic (Tc) are all stable in the high frequency region.

Next, the manufacturing method of this ceramic capacitor is demonstrated.

First, one or two or more selected from powdery SBZT, MnO ₂ , Bi ₂ O ₃ , PbO, and Sb ₂ O ₃ , glass frit, SiO ₂ , Al ₂ O ₃ , and a rare earth oxide were respectively weighed in a predetermined amount.

Here, Sr _0.95 Ba _0.05 (Zr _0.95 Ti _0.05 ) O ₃ , MnO ₂ , PbO, glass frit (ZnO-SiO ₂ -based glass or Li ₂ O-Al ₂ O ₃ -SiO ₂ -based glass), SiO ₂ , Al ₂ O ₃ and La ₂ O ₃ were basis weights as shown in Table 1.

Sample Number Main component (molar ratio) Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ Additive A (wt%) Additive B (wt%) Firing temperature (℃) Sr Ba Zr Ti MnO ₂ Al ₂ O ₃ SiO ₂ Glass frit Sb ₂ O ₃ Dy ₂ O ₃ One※ One 0 One 0 0 0 0 0 0 0 1050 2 One 0 One 0 0.3 0 0 0.5 1.0 0 1000 3 One 0 One 0 0.3 0 0 3.0 1.0 0 950 4※ One 0 One 0 0.3 0 0 11.0 1.0 0 950 5 One 0 0.95 0.05 5.0 0.1 0.05 2.5 0.5 0.01 950 6 * One 0 0.95 0.05 5.0 0.1 0.05 2.5 0.5 0.01 900 7 One 0 0.95 0.05 5.0 0.1 0.05 2.5 0.5 0.01 1000 8※ One 0 0.95 0.05 5.0 0.1 0.05 2.5 6.0 0.01 950 9 One 0 0.95 0.05 5.0 0.1 0.05 2.5 0.5 0.01 950 10 0.98 0.02 0.95 0.05 5.0 0.05 0.05 2.5 0.5 0.01 950 11 * 0.98 0.02 0.95 0.05 5.0 0.5 0.05 2.5 0.5 0.01 900 12 0.98 0.02 0.95 0.05 5.0 0.5 0.05 2.5 1.0 0.01 950 13 * 0.98 0.02 0.95 0.05 5.0 0.5 0.05 11.0 1.0 0.01 950 14 0.98 0.02 0.95 0.05 5.0 5.0 0.05 2.5 0.5 0.01 950 15 0.98 0.02 0.95 0.05 5.0 0.1 0.05 2.5 0.5 0.01 950 16 * 0.95 0.05 0.95 0.05 0.04 0 0 3.0 0 0 925 17 * 0.95 0.05 0.95 0.05 1.5 0 0 0.3 0 0 925 18 0.95 0.05 0.95 0.05 1.5 0 0 3.0 0 0 925 19 0.95 0.05 0.95 0.05 3 0.2 0.3 3.5 0.5 0.001 975 20 * 0.95 0.05 0.95 0.05 3 0.2 0.3 3.5 0.5 2.1 975 21 0.95 0.05 0.95 0.05 3 0.2 0.3 7.0 0.5 0.03 975 22 * 0.95 0.05 0.95 0.05 5 0.1 0.05 3.5 0.5 0.03 900 23 0.95 0.05 0.95 0.05 5 0.1 0.05 3.5 0.5 0.03 950 24 0.95 0.05 0.95 0.05 5 0.05 0.05 3.5 0.5 0.03 975 25 0.95 0.05 0.95 0.05 5 0.5 0.05 3.5 0.5 0.03 975 26 0.95 0.05 0.95 0.05 5 5.0 0.05 3.5 0.5 0.03 975 27 0.95 0.05 0.95 0.05 5 0.1 0.5 3.5 0.5 0.03 975 28 0.95 0.05 0.95 0.05 5 0.1 5.0 3.5 0.5 0.03 975 29 0.95 0.05 0.95 0.05 5 0.1 0.1 3.5 0.5 0.03 1050 30 * 0.95 0.05 0.85 0.15 3 0.2 0.3 3.5 0.5 0.03 975 31 0.8 0.2 0.95 0.05 5 0.1 0.05 3.5 0.5 0.03 950 32 * 0.8 0.2 0.95 0.05 5 0.1 0.05 5 0.5 0.03 900 33 * 0.75 0.25 0.95 0.05 5 0.1 0.05 3.5 0.5 0.03 950 ※ Out of the scope of the present invention

Next, these powders are put into a ball mill together with a predetermined amount of a dispersion medium such as water (or an organic solvent such as ethanol or acetone), mixed and ground for a predetermined period of time, for example, for 24 hours, and then dehydrated (or dewatered). And an organic solvent such as ethanol and deacetone) and dried. Samples of compositions other than the material composition of the present invention were also made and used as comparative examples (in Table 1, indicated by "※)).

Subsequently, the obtained dried powder was calcined at a temperature of 550 to 750 ° C for 0.5 to 5.0 hours, and then pulverized for 1 to 24 hours using Leicaigi (or automatic induction) to obtain a calcined powder having a predetermined particle size.

Next, a predetermined amount of organic binder was added to the calcined powder, and then uniformly mixed and assembled using a Leica group or the like to obtain a granulated powder (single granule) having a predetermined particle size. The organic binder was PVA (polyvinyl alchol) aqueous solution. As the organic binder, an ethyl cellulose aqueous solution, an acrylic resin solution (acrylic binder), or the like may be used.

Next, using a molding machine, the granulated powder is molded into pellets having a diameter of 20 mm and a thickness of 2 mm, and then calcined for 0.5 to 10.0 hours at a temperature of 925 to 1080 ° C. in the air, and the disk-shaped dielectric 1 of the present embodiment is formed. Got it. The sample of the material composition of this invention was baked at the temperature other than the baking temperature range of this invention, and it was set as the comparative example (in Table 1, a comparative example is shown with "*").

Table 2 shows the electrical properties in each sample. In addition, the comparative example is shown by "※" in Table 2.

Sample Number Relative permittivity ε Quality factor Q Specific resistance R (Ωcm) Temperature characteristic Tc (ppm / ℃) One※ 13 230 1.6 × 10 ¹¹ 96 2 17 680 1.7 × 10 ¹² 89 3 23 2300 1.9 × 10 ¹² 60 4※ 22 380 1.5 × 10 ¹² 180 5 26 2170 2.0 × 10 ¹² 45 6 * 20 410 1.8 × 10 ¹² 57 7 24 3060 2.1 × 10 ¹² 43 8※ 22 290 1.3 × 10 ¹¹ 62 9 25 4740 2.0 × 10 ¹² 39 10 23 2310 1.8 × 10 ¹² 29 11 * 14 220 1.5 × 10 ¹² 19 12 21 1760 1.9 × 10 ¹² 21 13 * 22 360 1.1 × 10 ¹² 43 14 20 1230 1.8 × 10 ¹² 36 15 22 2120 1.9 × 10 ¹² 34 16 * 21 380 1.7 × 10 ¹² 47 17 * 16 270 2.1 × 10 ¹² 31 18 22 2670 3.2 × 10 ¹² 56 19 29 2350 2.6 × 10 ¹² 41 20 * 25 640 1.9 × 10 ¹¹ 10 21 29 1800 2.1 × 10 ¹² 32 22 * 17 230 1.6 × 10 ¹¹ 85 23 31 2450 2.2 × 10 ¹² 75 24 25 3050 1.5 × 10 ¹² 61 25 30 3500 1.8 × 10 ¹² 82 26 34 2700 1.2 × 10 ¹² 97 27 30 2300 1.9 × 10 ¹² 74 28 29 1970 1.5 × 10 ¹² 23 29 31 4890 2.1 × 10 ¹² 35 30 * 41 470 1.2 × 10 ¹¹ -67 31 33 2120 1.9 × 10 ¹² 39 32 * 18 310 2.0 × 10 ¹² 19 33 * 42 150 1.9 × 10 ¹² 125 ※ Out of the scope of the present invention

Here, the relative dielectric constant? _Was measured under the conditions of 1 MHz and 1 V _rms at 25 ° C.

The quality factor (Q) was measured under the conditions of 1 MHz and 25 ° C. The temperature characteristic T _c measured the capacitance C 1 at 25 ° C. and the capacitance C 2 at 125 ° C., respectively, and substituted these measurements with the following equation to calculate the temperature characteristic T c.

Tc (ppmm / ℃)

= ((C2-C1) × 10 ⁶ ) / (C1 × (125-25))

The specific resistance (R (Ωcm)) measured the current value 1 minute after applying a DC voltage of 1000V at 25 ° C, and calculated the specific resistance from these voltage values and the current value.

As shown in these Table 2, according to the sample of this embodiment, it turns out that both the dielectric constant (epsilon), the quality coefficient (Q), and the temperature characteristic (Tc) are stable also in a high frequency range.

On the other hand, in the sample of the comparative example, compared with the sample of this embodiment, it turns out that any one of the dielectric constant (epsilon), the temperature characteristic (Tc), and the quality coefficient (Q) fell.

Moreover, when the surface state of the sample of this embodiment was observed using the metal microscope, it turned out that a space | gap etc. are not recognized at a grain boundary, and it became a compact sintered compact.

As described above, according to the ceramic capacitor of the present embodiment, the dielectric material 1 is made of SBZT, and is selected from 0.05 to 15% by weight of MnO ₂ and selected from Bi ₂ O ₃ , PbO, and Sb ₂ O ₃ . Or 0.001 to 5% by weight of two or more, 0.5-15% by weight of glass frit, 0.01-5% by weight of SiO ₂ , 0.01-5% by weight of Al ₂ O ₃ , to the cast product, if necessary, Since a material composition containing 0.001-2% by weight of rare earth oxide is used, high relative dielectric constant, good temperature characteristics, and high quality coefficient can be realized. Therefore, the characteristic can be stabilized in a high frequency band such as a microwave, and the reliability can be improved in the high frequency band.

According to the production process of the ceramic capacitor of this embodiment, the primary composition comprising the SBZT, the 0.05~15% by weight of MnO _2, Bi ₂ O _3, PbO, Sb ₂ O ₃ alone or in combination of two or more selected from the 0.001~ 5% by weight, adding 0.5-15 wt% of the glass composition, and 0.01-5% by weight of SiO ₂ in the main composition, as needed, from 0.01 to 5% by weight of Al ₂ O _3, 0.001-2% by weight of the rare earth oxide Since the added powder is shape | molded and it is made into a bulk molded object, and this molded object is baked at the temperature of 925-1080 degreeC, a compact and high strength sintered compact can be made by low temperature baking.

Second Embodiment

Fig. 2 is a diagram showing a multilayer ceramic capacitor according to a second embodiment of the present invention, wherein reference numeral 11 is a sheet-like dielectric layer, 12 is a thin internal electrode, and 13 and 14 are terminal electrodes.

In this multilayer ceramic capacitor, eight dielectric layers 11 and seven internal electrodes 12 are alternately stacked.

The dielectric layer 11 is a cast product made of SBZT, and 0.05 to 15% by weight of MnO ₂ , 0.001 to 5% by weight of one or two or more selected from Bi ₂ O ₃ , PbO, and Sb ₂ O ₃ , and glass frit. A sheet-like dielectric ceramic capacitor composed of a material composition to which 0.5 to 15% by weight of (glass composition) is added.

The material composition of the dielectric layer 11 is a material composition in which 0.01-5% by weight of SiO ₂ and 0.01-5% by weight of Al ₂ O ₃ are added to the cast product, or 0.001-2% by weight of rare earth oxide is added to the cast product. One of the material compositions or the material composition containing 0.01-5% by weight of SiO ₂ , 0.01-5% by weight of Al ₂ O _3, and 0.001-2% by weight of rare earth oxides may be used.

The internal electrodes 12 and the terminal electrodes 13 and 14 have characteristics as conductors and have a highly reliable electrode material such as Cu, Ni, W or Mo, or an alloy containing any two or more thereof. Or carbon, graphite, or mixtures thereof.

In this multilayer ceramic capacitor, the relative dielectric constant?, The quality factor Q, and the temperature characteristic Tc are all stable in the high frequency range.

Next, the manufacturing method of this multilayer ceramic capacitor is demonstrated.

First, one or two or more selected from powdery SBZT, MnO ₂ , Bi ₂ O ₃ , PbO, Sb ₂ O ₃ to form a material composition of the present embodiment, a glass composition, SiO ₂ , Al ₂ O ₃ , if necessary And a predetermined amount of rare earth oxide, respectively, these powders are put into a ball mill with a predetermined amount of a dispersion medium such as water (or an organic solvent such as ethanol or acetone), mixed and pulverized for a predetermined time, for example, for 24 hours. Then, dehydration (or deorganization solvent such as deethanol and deacetone) and drying were performed.

Next, after adding the organic binder and the organic solvent of predetermined amount to this dry powder, it knead | mixed using the Leicaigi, a kneading machine, etc., and made it the slurry which has a predetermined viscosity. Here, PVA (polyvinyl alcohol) aqueous solution was used as an organic binder. The organic binder may be an ethyl cellulose aqueous solution, an acrylic resin solution (acrylic binder), or the like.

Next, the slurry is molded into a sheet by a doctor blade method and degreased to form a green sheet, and an alloy or carbon containing Cu, Ni, W or MO, or any two or more thereof on the green sheet, A conductive paste made of a mixture of graphite, carbon and graphite as a conductive material was made into an internal electrode layer printed in a predetermined pattern.

As the conductive paste, a predetermined amount of an organic binder, a dispersant, an organic solvent, a reducing agent or the like is added to the Cu powder, and then kneaded. Carbon paste etc. using the mixed powder of can be used suitably.

Next, these green sheets are laminated in the thickness direction and pressed in the thickness direction to form a laminate.

Next, the laminate is fired in an inert gas atmosphere such as N ₂ gas or in an N ₂ -H ₂ reducing gas atmosphere at a temperature of 925 to 1080 ° C., and then terminal electrodes 13 and 14 are formed on both sides. It was.

As described above, a multilayer ceramic capacitor in which the dielectric layers 11 and the internal electrodes 12 are alternately stacked may be manufactured.

As described above, according to the multilayer ceramic capacitor according to the present embodiment, the dielectric layer 11 is formed of SBZT in a cast product containing 0.05 to 15% by weight of MnO ₂ , 1 selected from Bi ₂ O ₃ , PbO, and Sb ₂ O ₃ . 0.001 to 5% by weight of species or two or more, 0.5-15% by weight of glass composition, 0.01-5% by weight of SiO ₂ , 0.01-5% by weight of Al ₂ O ₃ to the cast product, if necessary, Since a material composition containing 0.001 to 2% by weight of rare earth oxide is used, it is possible to realize a high dielectric constant, good temperature characteristics and high quality coefficients. As a result, characteristics can be stabilized in a high frequency region such as microwaves. It is possible to improve the reliability in the area.

According to the manufacturing method of the multilayer ceramic capacitor of the present embodiment, 0.001 to 1 or 2 or more selected from 0.05 to 15% by weight of MnO ₂ , Bi ₂ O ₃ , PbO, and Sb ₂ O ₃ , in a cast product made of SBZT. 5% by weight, the glass composition is added 0.5-15% by weight, 0.01-5 the SiO ₂ in the main composition as needed, by weight%, 0.01 to 5% by weight of Al ₂ O _3, a rare earth oxide 0.001-2% by weight of added An internal electrode layer is formed on one green sheet and the green sheet is laminated in the thickness direction to form a laminate, and the laminate is baked at an inert gas atmosphere or in a reducing gas atmosphere at a temperature of 925-1080 ° C. It is possible to use inexpensive base metals or carbonaceous materials as the material of 12) compared with precious metals such as Pt and Pd. Therefore, the cost reduction can be achieved without degrading a characteristic.

As mentioned above, although each embodiment of the dielectric magnetic composition of the present invention, the magnetic capacitor using the same, and the manufacturing method thereof is explained based on the drawings, the specific configuration is not limited to the above-described embodiments, and the scope does not depart from the gist of the present invention. Design changes are possible.

For example, in the multilayer ceramic capacitor according to the second embodiment, eight dielectric layers 11 and seven internal electrodes 12 are alternately stacked, but the size of each of the dielectric layers 11 and 12 is increased. The number of floors can be appropriately changed depending on the required capacity and characteristics.

According to the dielectric self-composition of the present invention in the form described above, in the casting formed of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ ₁ , 0.9 ≦ _y ≦ 1), High relative dielectric constant because 0.05-15 wt% of MnO ₂ , 0.001-5 wt% of one or more selected from Bi ₂ O ₃ , PbO, Sb ₂ O ₃ , and 0.5-15 wt% of the glass composition were added. It is possible to realize good temperature characteristics and high quality coefficients. As a result, the characteristics can be stabilized in the high frequency region such as microwaves and the reliability can be improved in the high frequency region.

According to the magnetic capacitor of the present invention, since electrodes are formed on both surfaces of the element made of the dielectric magnetic composition of the present invention, the dielectric loss can be reduced in the high frequency band. As a result, the characteristic can be stabilized in a high frequency band such as a microwave and the reliability can be improved in the high frequency band.

In addition, using an inexpensive nonmetal or carbon-based material as the electrode can reduce the manufacturing cost without deteriorating the characteristics.

According to another magnetic capacitor of the present invention, since the sheet-like dielectric made of the dielectric magnetic composition of the present invention and the electrodes are alternately stacked, the dielectric loss can be reduced in the high frequency band. As a result, the characteristic can be stabilized in a high frequency band such as microwaves, and the manufacturing cost can be reduced without improving reliability in the high frequency band.

In addition, since it can be fired at a temperature of 925 to 1080 ° C, it is possible to use an inexpensive nonmetal or carbon-based material for the internal electrode, and the manufacturing cost can be reduced without degrading the characteristics.

According to the method for producing a dielectric magnetic composition of the present invention, MnO is used in a casting formed of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ ₁ and 0.9 ≦ _y ≦ 1). ₂ to 0.05 to 15% by weight, one or two or more selected from Bi ₂ O ₃ , PbO, Sb ₂ O ₃ , 0.001 to 5% by weight, the bulk of the powder to form a powder comprising 0.5-15% by weight of the glass composition Alternatively, the molded article is formed into a sheet, and the molded article is fired at a temperature of 925 to 1080 ° C., so that a compact and high-strength sintered compact can be obtained at low temperature at low temperatures.

According to another method for producing a dielectric ceramic composition of the present invention, an electrode is formed on one main surface of a sheet-shaped molded article, the molded articles are laminated in a plurality of thickness directions and pressed to form a laminate, and the laminate is then heated at the above temperature. Because of the sintering, inexpensive non-metals such as Cu and Ni, or carbon-based materials such as amorphous carbon and graphite can be used for the internal electrode material, compared to precious metals such as Pt and Pd. Can be obtained.

Claims (20)

0.05 to 15% by weight of MnO ₂ and Bi ₂ O ₃ in a cast product consisting of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ ₁ and 0.9 ≦ _y ≦ 1) , PbO, Sb ₂ O ₃ One or two or more selected from 0.001 to 5% by weight of the dielectric composition, characterized in that the glass composition by adding 0.5-15% by weight. The dielectric ceramic composition according to claim 1, wherein 0.01-5% by weight of SiO ₂ and 0.01-5% by weight of Al ₂ O ₃ are added to the cast product. The dielectric ceramic composition according to claim 1, wherein the main component is added with 0.001-2% by weight of a rare earth oxide. 3. The dielectric ceramic composition according to claim 2, wherein the main composition is obtained by adding 0.001-2% by weight of a rare earth oxide. The dielectric ceramic composition of claim 1, wherein the glass composition is a ZnO—SiO ₂ based glass or a Li ₂ O—Al ₂ O ₃ —SiO ₂ based glass. The dielectric ceramic composition of claim 2, wherein the glass composition is a ZnO—SiO ₂ based glass or a Li ₂ O—Al ₂ O ₃ —SiO ₂ based glass. 4. The dielectric magnetic composition of claim 3, wherein the glass composition is a ZnO-SiO ₂ -based glass or a Li ₂ O-Al ₂ O ₃ -SiO ₂ -based glass. The dielectric ceramic composition of claim 4, wherein the glass composition is a ZnO—SiO ₂ based glass or a Li ₂ O—Al ₂ O ₃ —SiO ₂ based glass. The method of claim 3, wherein the rare earth oxide, La ₂ O ₃ , CeO ₂ , Pr ₆ O ₁₁ , Nd ₂ O ₃ , Sm ₂ O ₃ , Dy ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , Tm Dielectric self-composition, characterized in that one or two or more selected from ₂ O ₃ , Yb ₂ O ₃ The method of claim 4, wherein the rare earth oxide, La ₂ O ₃ , CeO ₂ , Pr ₆ O ₁₁ , Nd ₂ O ₃ , Sm ₂ O ₃ , Dy ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , Tm Dielectric magnetic composition, characterized in that one or two or more selected from ₂ O ₃ , Yb ₂ O ₃ . A magnetic capacitor formed by forming electrodes on both surfaces of an element made of the dielectric magnetic composition according to claim 1. A magnetic capacitor formed by forming electrodes on both surfaces of an element comprising the dielectric ceramic composition according to claim 2. A magnetic capacitor formed by forming electrodes on both surfaces of an element made of the dielectric magnetic composition according to claim 3. A magnetic capacitor formed by forming electrodes on both sides of an element made of the dielectric magnetic composition according to claim 4. A magnetic capacitor formed by forming electrodes on both surfaces of an element made of the dielectric magnetic composition according to claim 5. A magnetic capacitor formed by alternately stacking a sheet-like dielectric composed of the dielectric magnetic composition according to claim 11 and an electrode. The magnetic capacitor of claim 11, wherein the electrode is made of a nonmetal or a carbon-based material. The magnetic capacitor of claim 12, wherein the electrode is made of a nonmetal or a carbon-based material. 0.05 to 15% by weight of MnO ₂ and Bi ₂ O ₃ in a cast product consisting of Sr _x Ba _1-x (Zr _y Ti _1-y ) O ₃ (where 0.8 ≦ _x ≦ ₁ and 0.9 ≦ _y ≦ 1) , PbO, Sb ₂ O ₃ One or two or more selected from 0.001 to 5% by weight of the powder, 0.5-15% by weight of the glass composition is molded to form a bulk or sheet-like molded article, this molded article is 925 A method of producing a dielectric magnetic composition comprising firing at a temperature of ˜1080 ° C. 20. The dielectric according to claim 19, wherein an electrode is formed on one main surface of the sheet-shaped molded body, and then the molded bodies are laminated and pressed in a plurality of thickness directions to form a laminated body, and the laminated body is fired at the above temperature. Method of producing a magnetic composition.